High-Performance Rechargeable Batteries with Fast Solid-State Ion Conductors

ABSTRACT

A high-performance rechargeable battery using ultra-fast ion conductors. In one embodiment the rechargeable battery apparatus includes an enclosure, a first electrode operatively connected to the enclosure, a second electrode operatively connected to the enclosure, a nanomaterial in the enclosure, and a heat transfer unit.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims benefit under 35 U.S.C. §119(e) of U.S.Provisional Patent Application No. 61/246,018 filed Sep. 25, 2009,entitled “Novel High-Performance Rechargeable Batteries with FastSolid-State Ion Conductors,” the disclosure of which is herebyincorporated by reference in its entirety for all purposes.

STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSOREDRESEARCH AND DEVELOPMENT

The United States Government has rights in this invention pursuant toContract No. DE-AC52-07NA27344 between the United States Department ofEnergy and Lawrence Livermore National Security, LLC for the operationof Lawrence Livermore National Laboratory.

BACKGROUND

1. Field of Endeavor

The present invention relates to batteries, and more particularly to,high-performance rechargeable batteries with fast solid-state ionconductors.

2. State of Technology

Electrochemical energy storage is required for grid storage, wirelesscommunications, portable computing, and will be essential for therealization of future fleets of electric and hybrid electric vehicles,which are now believed to be an essential part of the world's strategyfor reducing our dependence on oil, and minimizing the impact of gaseousemissions of CO₂ on global warming. In looking at those possiblematerials that can be used for anodes in electrochemical energyconversion and storage systems, hydrogen and lithium have the highestspecific capacities (Ah/kg). Hydrogen is of course used to power fuelcells, while lithium is used in advanced rechargeable batteries.

Most state of the art energy storage systems use lithium ion batterychemistry, with graphite anodes that intercalate lithium upon charging,mixed transition metal oxide cathodes that intercalate lithium duringdischarge, a micro-porous polyethylene electrode separator, andelectrolyte formed from a dielectric mixed solvent composed of organiccarbonates and high-mobility lithium salts. The movement of the lithiumions between the intercalation anodes and cathodes during charge anddischarge is known as the “rocking chair” mechanism.

Cells with liquid electrolytes are usually contained in cylindrical orprismatic metal cans, with stack pressure maintained by the walls of thecan, while cells with polymer gel electrolytes are usually contained insoft-side aluminum-laminate packages, with stack pressure achievedthrough thermal lamination of the electrodes and separators, therebyforming a monolithic structure.

The active graphite or transition metal oxide materials used in theelectrodes exist as fine powders, coated onto thin metal foils of copperand aluminum, respectively, and held in place by a PVDF binder. Bothnatural and manmade graphite such as MCMB have been used for the anodes,while Li_(x)CoO₂, LiNiO₂, Li,Mn₂O₄, mixed transition metal oxides withcobalt, nickel and manganese, and iron-phosphates are common choices forthe cathode.

Over the past decade, these systems have attained outstanding specificenergy and energy density, exceptional cycle life and rate capabilitiesthat enable them to now be considered for both vehicular and power toolapplications, in addition to their early applications in wirelesscommunications and portable computing. The best commercially available,polymer-gel lithium ion battery now has a specific energy of 180 to 200Wh/kg, an energy density of 360 to 400 Wh/L, and a reasonably good ratecapability, allowing discharge at C/2 or better.

Both liquid prismatic and polymer gel cells have been incorporated intolarge high-capacity power packs and used to power the mobile electricvehicles. Such high capacity systems have state-of-the-art computerizedcharge and discharge control, which includes graphical user interfaces,sensing for monitoring the health of individual cells, and chargebalancing networks.

Such lithium ion batteries, which rely on the rocking chair mechanism,are generally believed to be safer than those where lithium exists inthe reduced metallic state. However, the use of flammable liquid-phaseand two-phase polymer gel electrolytes, coupled with a high energydensity, a relatively delicate 20-micron thick polymeric separator, andthe possibility of lithium plating and dendrite formation due tonon-uniform stack pressure and electrode misalignment has led to safetyproblems with these energy storage systems. The possibility of such anevent occurring on commercial airliners, where many passengers carrylaptop computers and cell phones with such batteries, is especiallydisconcerting. These events have occurred on much larger scale, and havecaused industry-wide concern in the continued use of this importanttechnology.

Adequate and intelligent thermal management in these cells is essential.High rates of charge or discharge drives the temperature upward due toresistive heating of the electrolyte. When the core temperature of thesecells exceeds approximately 150° F., the systems frequently becomeunstable, with the possible initiation of autocatalytic reactions, whichcan lead to thermal runaway and catastrophic results. Disproportionationof the transition metal oxides can liberate sufficient oxygen to supportoxidation of the organic carbonate solvents used in the liquid orpolymer-gel electrolytes. It is now recognized that while conventionalsystems provide high energy density, their safety remains problematic.

The treatise, Introduction to Nano technology, by Charles P. Poole, Jr.,and Frank J. Owens. John Wiley &. Sons, 2003, states: “Nanotechnology isbased on the recognition that particles less than the size of 100nanometers (a nanometer is a billionth of a meter) impart tonanostructures built from them new properties and behavior. This happensbecause particles which are smaller than the characteristic lengthsassociated with particular phenomena often display new chemistry andphysics, leading to new behavior which depends on the size. So, forexample, the electronic structure, conductivity, reactivity, meltingtemperature, and mechanical properties have all been observed to changewhen particles become smaller than a critical size.”

SUMMARY

Features and advantages of the present invention will become apparentfrom the following description. Applicants are providing thisdescription, which includes drawings and examples of specificembodiments, to give a broad representation of the invention. Variouschanges and modifications within the spirit and scope of the inventionwill become apparent to those skilled in the art from this descriptionand by practice of the invention. The scope of the invention is notintended to be limited to the particular forms disclosed and theinvention covers all modifications, equivalents, and alternativesfalling within the spirit and scope of the invention as defined by theclaims.

The present invention provides a high-performance rechargeable batteryusing ultra-fast ion conductors. In one embodiment, the presentinvention provides high-performance rechargeable batteries based uponultra-fast solid-state ion conductors. The present invention will helpthe creation of a completely solid-state alternative to liquid-filledand polymer-gel lithium ion batteries. The scientific and technologicaladvancement of the present invention will assist in enabling dramaticperformance enhancements through the reduction of inert materials in thebattery; huge improvements in safety through the elimination offlammable organic liquids; U.S. dominance in advanced battery technologythrough the introduction of a disruptive technology; and help secure thefuture of the U.S. automotive industry, which includes electricvehicles.

The present invention will also help result in the creation of aroom-temperature sodium-beta (or equivalent) battery for electrical gridmanagement and transportation. Additional scientific and technicaladvancement of the present invention will enable load leveling forbetter utilization of power from fossil and nuclear plants; introductionof power from green sources such as wind and solar that arecharacterized by fluctuations from day-tonight, and fromseason-to-season; and utilization of the benefits of sodium-betabatteries for such applications, without the heat losses associated withhigh-temperature operation, and without the need for thermal insulationwhich increases the volume required by such energy storage devices.

The present invention will also help provide a completely solid-statealternative to lithium ion batteries and a room-temperature alternativeto conventional sodium-beta batteries, rely on solid-state fastion-conductors. The present invention will therefore drive thedevelopment of new solid-state ion conductors. Some specificquantifiable goals of one embodiment of the present invention that willguarantee adoption of these next-generation technologies are to: developone or more inherently safe, high-performance rechargeable batteriesbased upon ultra-fast solid ion conductors; develop viable energystorage devices with solid-state electrolytes with specific energiesranging from 500 to 2500 Wh/kg, thereby achieving as much as an order ofmagnitude enhancement in energy storage capability; eliminate the needfor volatile flammable organic solvents for electrolytes, to the extentpossible; and develop room-temperature variants of the high-temperaturesodium-beta batteries now used for electrical grid management, andtransportation.

The present invention has use in intelligent grid management for energysecurity, safe electric vehicles with dramatic range extension andenergy storage. The present invention also has use in energy storage forbattle field applications, including military bases, silent watch,propulsion for ships, directed energy weapons and other applications.The present invention has exceptional specific energy (ultimately,several times greater than that of conventional Li-ion batteries), isintrinsically safe, exhibits long cycle life due to exceptionalreversibility and dimensional stability, and can operate at roomtemperature.

The invention is susceptible to modifications and alternative forms.Specific embodiments are shown by way of example. It is to be understoodthat the invention is not limited to the particular forms disclosed. Theinvention covers all modifications, equivalents, and alternativesfalling within the spirit and scope of the invention as defined by theclaims.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated into and constitute apart of the specification, illustrate specific embodiments of theinvention and, together with the general description of the inventiongiven above, and the detailed description of the specific embodiments,serve to explain the principles of the invention.

FIG. 1 illustrates one embodiment a rechargeable battery of the presentinvention.

FIG. 2 illustrates another embodiment a rechargeable battery of thepresent invention.

FIG. 3 illustrates yet another embodiment a rechargeable battery of thepresent invention.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

Referring to the drawings, to the following detailed description, and toincorporated materials, detailed information about the invention isprovided including the description of specific embodiments. The detaileddescription serves to explain the principles of the invention. Theinvention is susceptible to modifications and alternative forms. Theinvention is not limited to the particular forms disclosed. Theinvention covers all modifications, equivalents, and alternativesfalling within the spirit and scope of the invention as defined by theclaims.

The present invention provides a rechargeable battery. The rechargeablebattery includes an enclosure, a first electrode operatively connectedto the enclosure, a second electrode operatively connected to theenclosure, a nanomaterial in the enclosure, and a heat transfer unit.

The nanomaterial is defined as: nanomaterial+dielectric. A wide range ofnanoparticles can be used. For example the following nanoparticles canbe used: metal and metal alloy particles for anodic dissolution andthermal transport; hydrides as source of hydrogen ions; lithium andlithium alloys; intercalated graphite and carbon aerogel as Li source(anodic material); intercalated transition metal oxide as Li sink(cathodic material); and semiconductors for photovoltaic conversion inphoto-electrochemical or hybrid electrochemical cell.

The particle suspension is defined as: particlesuspension=particles+dielectric or ionic fluid. A wide range ofparticles can be used. For example the following particles can be used:metal and metal alloy particles for anodic dissolution and thermaltransport; hydrides as source of hydrogen ions; lithium and lithiumalloys; graphite intercalated with lithium; and carbon aerogel with acoating of lithium as a lithium source (anodic material); intercalatedtransition metal oxides as lithium sink (cathodic material); andsemiconductors for photovoltaic conversion in photo-electrochemical orhybrid electrochemical cell.

Nanoparticles or particles for the nanomaterial anolyte can be made ofpure elemental materials including Pb, Cd, Zn, Fe, Na, Ca, Mg, Al, andLi, as well as any alloy formed from these pure elemental materials. Inthe case of a nanofluid flow cell using lithium-ion type chemistry, thenanoparticles in the anolyte could be Li-intercalated natural graphite,Li-intercalated synthetic graphite, Li—S; alloys, Li—Sn alloys, or otherLi-containing alloys or compounds. Similar compositions can be used forparticles suspensions. In the case of a nanofluid flow cell usinglithium-ion type chemistry, the nanoparticles in the catholyte could bea transition metal oxide such as Li_(x)CoO₂, Li_(x)NiO₂, Li_(x)Mn₂O₄, amixed transition metal oxide such as Li_(x)(Co, Ni, Mn)O₂, or aphosphate such as Li_(x)FePO₄. Similar compositions can be used forparticle suspensions. Hydrides can also be used for anolytenanoparticles or particles.

Referring now to the drawings and in particular to FIG. 1, a solid-statecell for on-chip applications is illustrated. The cell is designatedgenerally by the reference numeral 100. Metal-air batteries provideadvantages over systems where both reactants are carried with the deviceas payload. Since the systems are air breathing, taking one of thereactants from the atmosphere, they are able to provide large advantagesin regard to energy density and specific energy. The present inventionshould be able to achieve 2500 Wh/kg, with a limit of approximately 5000Wh/kg. Typically the electrochemical dissolution of a metal anode isdepolarized by oxygen reduction at an air-breathing cathode.Unfortunately, these systems lack the reversibility required to serve asrechargeable batteries, and are usually used as primaries.Alternatively, mechanically refueling can be used, where anode materialis continuously fed to the system.

Metal air batteries of the present invention can be built that areentirely analogous to solid oxide fuel cells. In these systems, YSZ(Y₂O₃-stabilized ZrO₂) electrolytes are be used, with the formation ofoxygen anions at the outer surface of the YSZ at a porous catalyticmetal electrode, such as platinum, and then transported through the YSZto the anode compartment, where they react with metal cations to formoxides. One possibility is a high-temperature lithium-air battery.Rechargeability requires reversibility of the oxide-formation at theYSZ/anode interface. By using low-melting eutectics, the anode can bekept in liquid phase at ambient temperature, and oxides can be bathed inthe molten metal, with the possibility of dimensional stability of theelectrode, and reversibility of the oxidation reaction between theoxygen anions and the metal cations.

Sodium-Beta Batteries

Sodium-beta batteries are crucial energy storage devices that relyheavily on solid-state fast ion conductors. In general, these batterieshave a molten sodium anode and a 3″-alumina, sodium-ion conductive,high-temperature solid-state electrolyte and separator. Two variantsexist, known as sodium/sulfur and sodium/metal-chloride cells. Thesodium/metal-chloride battery is also known as the ZEBRA battery.

Background on Na—S Battery

The most well developed sodium-beta battery is the Na—S system, whichuses a sodium ion-conductive electrolyte, operating at a hightemperature to maintain the sodium anode and the sulfur cathode in amolten state. During discharge, the molten Na is oxidized at theNa/β″-Al₂O₃, forming Na+ ions. These ions migrate through the β″-Al₂O₃electrolyte, which is usually in the form of a ceramic tube. Thebeta-alumina solid electrolyte is sometimes referred to as BASE.

After diffusion through the (3″-Al₂O₃ separator, Na″ ions combine withsulfur reduced at the positive electrode, thereby forming sodiumpentasulfide (Na₂S₅), which is immiscible with the remaining moltensulfur. A two-phase system is therefore formed during the initial stageof discharge. After all of the free sulfur is converted to Na₂S₅ duringthe initial stage of discharge, the cell enters a second stage ofdischarge, with the formation of single-phase polysulfides with highersulfur content (Na₂S_(x), where x=2.7 to 5). If discharge continues, thecell enters the third stage with the formation of a second two-phasesystem consisting of residual Na₂S, and Na₂S₂. Most cells are designedto prevent the formation of Na₂S₂ during such over discharge.

Stationary Power Applications

The sodiumisulfur (Na—S) battery has enjoyed widespread use forstationary applications, such as grid management. As pointed out by theCalifornia Energy Commission during their Energy Storage Workshop, inthe presentation entitled Overview of Na—S Battery for Load Management,this generic type of battery is potentially very useful for electricalgrid applications. Multi-megawatt class systems have been built anddeployed. With the increasing uses of green sources of energy, such assolar, wind and tidal, with variable production rates, the need forreliable energy storage on the grid is becoming even greater.

The Na—S battery is very similar to the ZEBRA battery, and has enjoyedwidespread use for stationary applications, such as grid management. Aspointed out by the California Energy Commission during their EnergyStorage Workshop, in the presentation entitled Overview of Na—S Batteryfor Load Management, this generic type of battery is potentially veryuseful for electrical grid applications. With the increasing uses ofgreen sources of energy, such as solar, wind and tidal, with variableproduction rates, the need for reliable energy storage on the grid isbecoming even greater.

Background on ZEBRA

The ZEBRA cell is considered to be a variant of the sodium-beta typesince it also has a molten sodium anode and a 13″-alumina, sodium-ionconductive, high-temperature solid-state electrolyte and separator, andis also referred to as a Na—NiCl₂ cell. Applications for the ZEBRAbattery include a variety of electric vehicles, such as delivery vans,taxis, school buses, passenger cars, surface ships and submarines, andstationary applications similar to those for the Na—S cell

The ZEBRA battery was invented in 1985 by a group led by Dr. JohanCoetzer at the CSIR in Pretoria, South Africa, and is generallyconsidered safer and more robust due to the replacement of the moltensulfur electrode with a metal/metalchloride electrode. Some authorsstate that the ZEBRA name stands for the “Zeolite Battery ResearchAfrica Project” which developed the technology, which seems mostreasonable, while other authors state that ZEBRA name stands for “ZeroEmission Battery Research Activities.”

The ZEBRA cell is considered to be a variant of the sodium-beta typesince it has a molten sodium anode and a (13″-alumina, sodium-ionconductive, high-temperature solid-state electrolyte and separator, andis also referred to as a Na—NiCl₂ cell. The ZEBRA cell has an opencircuit voltage of 2.58 volts, and consists of a molten sodium anode, anelectrolyte of NaAlCl₄, which melts at 160° C. (320° F.) and freezes at157° C. (315° F.), a sodium-ion conducting 3″-Al₂O₃ separator, and aNiCl₂/Ni cathode. The shorthand notation for the ZEBRA cell is:Na/β″-Al₂O₃/ NaAlCl₄/NiCl₂/Ni. The range of operating temperature forthis battery is given as 270° C. (517° F.) to 350° C. (662° F.). Thisbattery technology had achieved a specific energy of 85 Whlkg and aspecific power 150 W/kg.

Goals for Development of Disruptive Energy Storage Technology

Specific goals are: (1) to develop one or more inherently safe, highperformance rechargeable batteries based upon ultra-fast solid ionconductors; (2) identify viable pathways to specific energies rangingfrom 1000 to 5000 Wh/kg thereby achieving as much as an order ofmagnitude enhancement in energy storage capability; and (3) wherepossible, eliminate the need for volatile flammable organic solvents forelectrolytes. Such technology would provide an attractive and enablingalternative for advanced electric vehicles for domestic and militaryapplications, as well as for mobile directed energy weapons.

Development of Solid-State Fast Ion Conductors for Advanced BatterySystems

The lithium-ion battery is mature, with a specific energy that is notexpected to increase substantially above 200 Wh/kg, and is plagued withsafety issues associated with the flammable organic solvents used in theliquid and polymer gel electrolytes, and gaseous products from firessuch as HF. The ZEBRA battery is an inherently safe alternative, butrequires a high operating temperature, between 270° C. and 350° C.Thermal insulation necessary for high temperature operation can limitenergy losses from the battery to between 10% and 25% of the storedenergy, but lower the energy density substantially.

Work is proposed here to systematically explore new cell chemistriesthat promise to provide substantially greater specific energy and energydensity than either modern lithium-ion systems, or the sodium-beta(ZEBRA) battery, using the fastest solid-state ion-conductors known toreplace liquid-phase electrolytes. Such solid state electrolytes includematerials such as Lii (cep), a-Agl (bee), RbAg₄1₅ (distorted cubic),(3″-A1203 (spine] blocks) and Y₂O₃-stabilized ZrO₂. Note that the ioniccrystal with the highest known ion conductivity is RbAg₄I₅. These aresummarized below:

Silver Iodide (Mobile Ag)

-   -   T<146° C. y-Agl (Zinc Blende) & (3-Agl (Wurtzite)        -   T>146° C.-*a-Agl (Body Centered Cubic)-*a-100 S m′

Rubidiuim-Substituted Silver Iodide (Mobile Ag′)

-   -   T 25° C.-RbAg₄l₅ (Fixed I & Rb; Mobile Ag)-cr-25 S m-′    -   Activation Energy for Flopping r., 0.07 eV    -   Solid-State Battery: Ag & RbI3 Electrodes

Beta Alumina (Mobile Na)

-   -   T 300° C.-*R″-(A1₂O₃)₁₁(Na₂O), (Spine] Blocks)->a 10 S m-′        -   Sodium-Sulfur Cell: Na Anode & Sulfur Cathode

Stabilized Cubic Zirconia (Mobile O²⁻)

-   -   T 900° C.-(ZrO₂)₉(Y₂O₃)₁ (Cubic)—6—1 S m-′    -   T . . . ,500° C.—a (ZrO₂)_(85.72)(CaO)₁₅₋28 (Cubic)—a 6—500 S        n11    -   Oxygen Sensor & Solid Oxide Fuel Cell: 02 Cathode & H2 Anode

To achieve rate capabilities comparable Li-ion batteries, solid-stateelectrolytes that have ion conductivities comparable to the liquid-phaseelectrolytes are used. The Li-based sold-state electrolyte with the bestperformance appears to be L_(10.3610)1_(4O0.007P0.11S0.38) with aconductivity of 0.5 mS/cm at ambient temperature, though non Li-basedcompounds are seen that exceed this bench-mark by great margin.

EXAMPLE(S)

One embodiment of the present invention includes construction ofpractical three-dimensional cell architectures with solid-state fast ionconducting electrolytes and completely reversible, dimensionally-stableliquid electrodes, with the demonstration of a I Ah cell including thefollowing steps:

Coating nanostructural material such as carbon with materials necessaryfor metal-halogen electrode (Fe/FeCl₂, Ni/NiCl₂, Ag/AgCl, Ag1Agl,Rb/RbI, Rb/RbI_(3s) etc.) using appropriate techniques, which mayinclude CVD, PVD, including but not limited to ALD.

Overcoating of the resultant structure with appropriate film and/orcoating of solid-state fast ion conductor. If insurmountable dimensionalstability problems are encountered with homogenous inorganicion-conducting films, a coating with dispersed particles with apolymeric binder can be used.

Infiltration of the pore structure with liquid-phase low-meltingeutectic metal anode, thereby forming the second electrode in a uniquethree-dimensional battery system with unparalleled rate capability, andnone of the problems of self shielding usually encountered with porouselectrode systems.

Performance testing of three-dimensional system with novel low-meltingeutectic metal electrode infiltrated into pores of nanostructuralbattery.

Applications in Terrestrial Vehicles

Applications for these rechargeable batteries have focused primarily ontheir potential used in electric vehicles, including delivery vans,taxis, ships and submarines. Individual cells with the nominal cellvoltage of 2.58 volts and capacity of 32 Ah have been configured inseries-parallel arrays, thereby achieving an OCV of 300 volts. Modulevoltages from 24 to 1000 volts, and module stored energy of 2 to 50 kWhare discussed in the literature.

Surface Ship and Submarine Applications

Despite the history of the lead acid battery (LAB) in marine andsubmarine applications, it is considered to be somewhat unreliable.Problems are still encountered with short circuits that can lead toself-discharge, sudden-death and cell replacement. The failure of asingle cell can significantly degrade the overall performance of alarger battery.

In marine and submarine applications, the ZEBRA battery appears to alloythe battery, once charged, to retain 100% of its charge, regardless ofwhether the battery is maintained at its operating temperature, orallowed to cool down (to a frozen state). From a mission readinesspoint-of-view, it is conceivable that the batteries on a submarine couldbe charge to 100% SOC, and then placed in a frozen state for a period ofyears. With a 24-hour heating period, the cells would be ready to go.

Example—Air or Oxygen Breathing Battery

An example of an electro-chemical energy conversion and storage systemconstructed in accordance with the present invention is illustrated inFIG. 2. The air or oxygen breathing nanofluid or particle suspensionflow battery is designated generally by the reference numeral 200. Theair or oxygen breathing nanofluid or particle suspension flow battery200 includes the following components: electro-catalytic anode 201,nanofluid or particle suspension anolyte 202, nanofluid or particlesuspension anolyte storage tank & heat transfer 203, heat rejection 204,electrolyte & separator 205, oxygen cathode 206, oxygen or air 207,selective transport of molecular oxygen 208, oxygen selective membrane209, load 210, pump 211, fluid lines 212, electrical connectors 213, andhousing 214. The housing is made at least in part of a non-conductivematerial. The air or oxygen breathing nanofluid or particle suspensionflow battery 200 provides a new inherently safe, high-energy, high-raterechargeable battery.

The air or oxygen breathing nanofluid or particle suspension flowbattery 200 includes electro-oxygen cathode 206, and electro-catalyticanode 201. The electro-oxygen cathode 206 and electro-catalytic anode201 are electrically connected across load 206 by electrical connectors213.

Oxygen or air 207 provides selective transport of molecular oxygen 208through oxygen selective membrane 209 to electrolyte and separator 205.

The nanofluid or particle suspension anolyte 202 is contained withinhousing 214 adjacent oxygen cathode 206 and electro-catalytic anode 201.

The electro-catalytic anode 201 gives up electrons at a potential abovethat of the electro-oxygen cathode 206. The conductive link via the load210 through electrical connectors 213 carries electrons from theelectro-catalytic anode 201 to the electro-oxygen cathode 206. Thenanofluid or particle suspension anolyte 202 dissociates ions. Theseions serve to deliver electrons and chemical matter through thenanofluid or particle suspension anolyte 202 to balance the flow ofelectric current through the load 210 during operation.

The nanofluid or particle suspension anolyte 202 is circulated to ananofluid or particle suspension anolyte storage tank and heat transferunit 203 through fluid lines 212 by pump 211. Nanofluid or particlesuspension suspension anolyte storage tank and heat transfer unit 203provides heat rejection 204. The nanofluid or particle suspensionanolyte 202 is a nanofluid or particle suspension.

The nanofluid is defined as: nanofluid=nanoparticles+dielectric or ionicfluid. A wide range of nanoparticles can be used. The particlesuspension is defined as: particle suspension=particles+dielectric orionic fluid. A wide range of particles can be used.

Referring now to FIG. 3, a suitable solid-state fast ion conducting filmis deposited over the interdigitated 2D electrodes with chemical vapordeposition (CVD), a physical vapor deposition (PVD) process such asthermal evaporation, electron beam evaporation, magnetron sputtering,and/or atomic layer deposition (ALD). Practical processes such asmulti-magnetron sputtering as a means of building high-performancethin-film thermoelectric devices, including super-lattices formed fromlow-melting and difficult to process semiconductors can be used. Thesame technology can be readily applied to the fabrication of thin-filmsolid-state energy storage devices.

A practical three-dimensional cell architecture has been obtained with asolid-state fast ion conducting electrolyte and completely reversible,dimensionally-stable liquid electrodes, with the demonstration of a I Ahcell. A nanostructural material such as carbon aerogel is coated withthose materials necessary for formation of an appropriate metal-halogenelectrode (Fe/FeC1₂, Ni/NiCl₂, AggAgCl, Ag/Agt, Rb/Rbl, Rb/Rbl₃, etc.),or another appropriate electrode, using techniques such as CVD, PVD, andALD. The resultant structure is then be over-coated with an appropriatefilm and/or coating of solid-state fast ion conductor. If insurmountabledimensional stability problems are encountered with homogenous inorganicion-conducting films, a coating with dispersed particles with apolymeric binder could be used. Finally, liquid-phase metallic alloys(low-melting eutectics) are infiltrated into the pore structure, therebyforming the second electrode in a unique three-dimensional batterysystem with unparalleled rate capability, and none of the problems ofself shielding usually encountered with porous electrode systems.Performance testing of the three-dimensional system, with novellow-melting eutectic metal electrode infiltrated into pores ofnanostructural battery, is performed. Ultimately, the cells are includedin the integration of three-dimensional cell architectures into larger10-Ah battery.

The graphitic intercalation anode (LiC₆) has a specific capacity of 372Ah/kg, a capacity density of 937 Ah/L, and a self-diffusion coefficientof approximately 10′⁹ cm /sec. The transition metal intercalationcathode (LiCoO₂) has a specific capacity of 274 Ah/kg, a capacitydensity of 1017 Ah/I, and a self-diffusion coefficient of approximately10⁻⁹ cm²/sec. These cells have now been developed to the point wherespecific energies of 180 to 200 W/kg and energy densities of 380-400Wh/L can be achieved. The OCV of these cells is approximately 3.1 volts,with a nominal operating voltage of 3.8 volts, and an end voltage ofapproximately 3.0 volts. Work during the past decade has now increasedthe charge-discharge cycle life of these cells to the point where 1500deep discharge cycles can be achieved (defined as the point where thecell capacity is 80% of the initial capacity immediately followingformation). Microporous polyolefin separators with thicknesses of about20 microns are easily penetrated by foreign objects and debris, or bylithium dendrites that can form during unplanned plating within thecells during cycling. The Li-ion systems continue to be plagues byserious safety issues with volatile and flammable organic solvents, withthe formation of hazardous vapors from such fires that include not onlyCO and C0₂, but also HF. Battery fires with these systems have proven tobe injurious, damaging, and very costly.

In general, systems relying on conventional liquid-filled, orpolymer-gel lithium ion batteries could benefit greatly from acompletely solid-state rechargeable battery. Such a battery would beavailable to achieve enhanced specific energy and energy density,through the elimination of an abundance of inert (non energy storingmaterials) present in the lithium-ion system, and would be able tooperate far more safely due to the elimination of volatile and flammableorganic solvents used in the electrolytes. While fast-ion conductorsexist, and have been used for very small on-chip rechargeable batteriesfor memory backup in computers and other electronic devices, nosolid-state battery exists that can be scaled up for applications inportable computing, wireless communications, electric vehicles, and thebattlefield needs of the soldier and sailor. The proposed work will seekto develop a completely solid-state alternative to the modernlithium-ion battery. This battery, if developed, will be to thelithium-ion battery what transistors and integrated circuits were to thevacuum tube.

Microporous polyolefin separators with thicknesses of about 20 micronsare easily penetrated by foreign objects and debris, or by lithiumdendrites that can form during unplanned plating within the cells duringcycling. The Li-ion systems continue to be plagues by serious safetyissues with volatile and flammable organic solvents, with the formationof hazardous vapors from such fires that include not only CO and CO₂,but also HF. Battery fires with these systems have proven to beinjurious, damaging, and very costly.

While the invention may be susceptible to various modifications andalternative forms, specific embodiments have been shown by way ofexample in the drawings and have been described in detail herein.However, it should be understood that the invention is not intended tobe limited to the particular forms disclosed. Rather, the invention isto cover all modifications, equivalents, and alternatives falling withinthe spirit and scope of the invention as defined by the followingappended claims.

1. A rechargeable battery apparatus, comprising: an enclosure, a firstelectrode operatively connected to said enclosure, a second electrodeoperatively connected to said enclosure, a suspended flowingnanomaterial in said enclosure, a solid-state fast ion conductor, and aheat transfer unit.
 2. The rechargeable battery apparatus of claim 1wherein said nanomaterial includes nanoparticles, a dielectric fluid,and dissolved ions for conduction.
 3. The rechargeable battery apparatusof claim 1 wherein said nanomaterial includes particles, a dielectricfluid, and dissolved ions for conduction.
 4. The rechargeable batteryapparatus of claim 2 wherein said nanoparticles are hydrides as a sourceof hydrogen ions.
 5. The rechargeable battery apparatus of claim 2wherein said nanoparticles are lithium or lithium alloys including Li—Sior Li—Sin alloys.
 6. The rechargeable battery apparatus of claim 2wherein said nanoparticles are intercalated graphite or carbon aerogelas a Li source.
 7. The rechargeable battery apparatus of claim 2 whereinsaid nanoparticles are intercalated transition metal oxide as a Lisource.
 8. The rechargeable battery apparatus of claim 1 including asecond enclosure, a pair of electrodes operatively connected to saidsecond enclosure, a second nanomaterial in said second enclosure, and asecond heat transfer unit.
 9. The rechargeable battery apparatus ofclaim 1 including an oxygen selective membrane and wherein said firstelectrode is an oxygen cathode
 10. The rechargeable battery apparatus ofclaim 1 including a particle supply operatively connected to saidenclosure that introduces nanoparticles or particles into said enclosureand a supply operatively connected to said enclosure that introduces adielectric into said enclosure.
 11. A rechargeable battery apparatus,comprising: an enclosure, a first electrode operatively connected tosaid enclosure, a second electrode operatively connected to saidenclosure, a nanomaterial in said enclosure, and a heat transfer unit.12. The rechargeable battery apparatus of claim 11 wherein saidnanomaterial includes nanoparticles and a dielectric.
 13. Therechargeable battery apparatus of claim 12 wherein said nanoparticlesare hydrides as a source of hydrogen ions.
 14. The rechargeable batteryapparatus of claim 12 wherein said nanoparticles are lithium or lithiumalloys.
 15. The rechargeable battery apparatus of claim 12 wherein saidnanoparticles are intercalated graphite or carbon aerogel as a Lisource.
 16. The rechargeable battery apparatus of claim 12 wherein saidnanoparticles are intercalated transition metal oxide as a Li source.